CN110844945A - High-nickel ternary cathode material and preparation method and application thereof - Google Patents
High-nickel ternary cathode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 140
- 239000010406 cathode material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 80
- 238000005245 sintering Methods 0.000 claims abstract description 56
- 239000007774 positive electrode material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 39
- 239000011247 coating layer Substances 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 238000011282 treatment Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000011268 mixed slurry Substances 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 78
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000011883 electrode binding agent Substances 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 229910010951 LiH2 Inorganic materials 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 229910006178 NixCoyMn(1-x-y)(OH)2 Inorganic materials 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000007580 dry-mixing Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- 229910013415 LiNixCoyMn(1-x-y)O2 Inorganic materials 0.000 description 1
- 229910013424 LiNixCoyMn(1−x−y)O2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
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- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a high-nickel ternary cathode material and a preparation method and application thereof. The method for preparing the high-nickel ternary cathode material comprises the following steps of: (1) mixing a high-nickel ternary positive electrode material precursor, a metal oxide and a lithium salt to obtain a mixed material; (2) sequentially carrying out first sintering treatment and second sintering treatment on the mixed material to obtain a first product; (3) mixing the first product with a hydrogen phosphate solution to enable the hydrogen phosphate to wrap the surface of the first product to obtain mixed slurry; (4) adding alkali liquor into the mixed slurry to enable the hydrogen phosphate to have a precipitation reaction and form a coating layer on the surface of the first product, so as to obtain a second product containing the coating layer; (5) and carrying out third sintering treatment on the second product to obtain the high-nickel ternary cathode material. The method can realize that the surface of the high-nickel ternary material is uniformly coated with the phosphate layer, thereby inhibiting the generation of NiO cubic phase on the surface layer of the high-nickel ternary cathode material and the collapse of the material structure, and improving the cycle performance and the thermal stability of the battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a high-nickel ternary cathode material and a preparation method and application thereof.
Background
The lithium ion secondary battery has the advantages of high specific capacity, high working voltage, wide working temperature range, long cycle life, no memory effect, no pollution, light weight, good safety performance and the like, thereby being widely applied to mobile equipment such as mobile phones, digital cameras, notebook computers and the like. With the development of science and technology, most products tend to be portable and economical, which requires the development of lithium ion battery products towards high energy density.
At present, cobalt has the defects of resource shortage, high price and the like, and lithium cobaltate has limited space for further improving the energy density of the battery. High nickel ternary material LiNixCoyMn(1-x-y)O2(x is more than or equal to 0.6) has the advantages of high capacity, stable cycle performance, low price and the like. However, in the circulation process of the layered ternary material battery, due to the erosion and catalysis of the electrolyte, with the continuous insertion and extraction of lithium ions, the transition metal ions in the high-nickel ternary material are dissolved out, and the high-nickel ternary material reacts with the electrolyte to generate gas, so that a large amount of NiO cubic phase is generated on the surface of the high-nickel ternary material. The NiO cubic phase electron and lithium ion have low conductivity, so that the battery impedance is rapidly increased, and the technical problems of reduction of the capacity and rate capability of the high-nickel ternary material battery, poor cycle performance and the like are caused. At present, the coating process of the high-nickel ternary material is dry coating, namely mixing metal oxide and the high-nickel ternary material, and then carrying out secondary sintering. Although the method has a simple process, the phenomenon of nonuniform coating is easy to occur, so that the high-temperature performance and high-temperature storage of the material are poor.
Therefore, the existing preparation process of the high-nickel ternary material needs to be further improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a method for preparing a high-nickel ternary cathode material, the high-nickel ternary cathode material prepared by the method and a lithium battery adopting the high-nickel ternary cathode material. The method can realize that the surface of the high-nickel ternary material is uniformly coated with the phosphate layer, thereby inhibiting the generation of NiO cubic phase on the surface layer of the high-nickel ternary cathode material and the collapse of the material structure, and improving the cycle performance and the thermal stability of the battery.
In one aspect of the invention, a method of making a high nickel ternary positive electrode material is provided. According to an embodiment of the invention, the method comprises: (1) mixing a high-nickel ternary positive electrode material precursor, a metal oxide and a lithium salt to obtain a mixed material; (2) sequentially carrying out first sintering treatment and second sintering treatment on the mixed material to obtain a first product; (3) mixing the first product with a hydrogen phosphate solution to enable the hydrogen phosphate to wrap the surface of the first product to obtain mixed slurry; (4) adding alkali liquor into the mixed slurry to enable the hydrogen phosphate to have a precipitation reaction and form a coating layer on the surface of the first product, so as to obtain a second product containing the coating layer; (5) and carrying out third sintering treatment on the second product to obtain the high-nickel ternary cathode material.
According to the method for preparing the high-nickel ternary cathode material, firstly, a metal oxide-doped high-nickel ternary cathode material inner core (namely a first product) is prepared by utilizing a high-nickel ternary cathode material precursor, a metal oxide and a lithium salt, then, a hydrogen phosphate is wrapped on the surface of the first product, and then, a hydrogen phosphate substrate on the surface of the first product is wrapped by utilizing an alkali liquor, so that a uniform and continuous phosphorus-containing coating layer is formed, and a second product containing the coating layer is obtained; and sintering to obtain the high-nickel ternary cathode material product with the metal oxide doped core and the phosphorus-containing coating layer. The method can realize that the phosphate layer is uniformly coated on the surface of the high-nickel ternary material, so that the contact between the electrolyte and the anode material is effectively isolated, the generation of NiO cubic phase on the surface layer of the high-nickel ternary anode material and the collapse of the material structure are inhibited, the cycle performance and the thermal stability of the battery are improved, and the method is simple and easy to control in process, strong in operability and easy to industrialize.
In addition, the method for preparing the high-nickel ternary cathode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the high nickel ternary positive electrode material precursor is NixCoyMn(1-x-y)(OH)2Or NixCoyAl(1-x-y)(OH)2Wherein, 0.6<x<0.85，0.1≤y<0.2。
In some embodiments of the invention, the metal oxide comprises a metal selected from MgO, Al2O3And ZrO2At least one of (a).
In some embodiments of the invention, the lithium salt comprises a compound selected from the group consisting of LiOH, LiNO3And Li2CO3At least one of (a).
In some embodiments of the present invention, a ratio of a total molar amount of the metal elements in the high-nickel ternary positive electrode material precursor to a molar amount of the lithium salt is 1 (1.03-1.08), and a molar amount of the metal oxide is 0.001-0.1% of the total molar amount of the metal elements in the high-nickel ternary positive electrode material precursor.
In some embodiments of the invention, in step (1), the mixing conditions comprise: the temperature is 20-30 ℃, the time is 10-40 min, and the stirring speed is 800-1200 r/min.
In some embodiments of the present invention, the first sintering treatment is performed at 450-550 ℃ for 4-6 hours, and the second sintering treatment is performed at 740-820 ℃ for 13-16 hours.
In some embodiments of the invention, the hydrogen phosphate salt comprises a hydrogen phosphate salt selected from LiH2PO4、Al(H2PO4)3And NaH2PO4At least one of (a).
In some embodiments of the invention, the concentration of the hydrogen phosphate solution is 15.0 to 20.0 wt%.
In some embodiments of the invention, the mass ratio of the hydrogen phosphate solution to the first product is (1-10): 90-100.
In some embodiments of the invention, the lye comprises at least one selected from the group consisting of an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution.
In some embodiments of the invention, in step (3), the mixing conditions comprise: the temperature is 30-50 ℃, the time is 20-30 min, and the stirring speed is 500-700 r/min.
In some embodiments of the present invention, the third sintering treatment is performed at 450 to 500 ℃ for 4.5 to 5.5 hours.
In some embodiments of the present invention, step (5) is preceded by: and washing, filtering and drying the second product in sequence.
In some embodiments of the invention, the wash filtration comprises: and washing the second product until the pH value of the filtrate is 6-7.
In some embodiments of the invention, the drying is performed at 80-120 ℃ for 16-20 hours.
In another aspect of the invention, a high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the high-nickel ternary cathode material is prepared by the method for preparing the high-nickel ternary cathode material in the embodiment. Therefore, the high-nickel ternary cathode material is provided with a metal oxide doped and modified high-nickel ternary cathode material core and a phosphorus-containing coating layer, the phosphorus-containing coating layer can effectively isolate the electrolyte from contacting with the cathode material, inhibit the generation of NiO cubic phase on the surface layer of the high-nickel ternary cathode material and the collapse of a material structure, and generate a synergistic effect with the metal oxide doping in the core, so that the cycle performance and the thermal stability of the battery are improved.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes: a positive electrode, a negative electrode, a separator and an electrolyte; wherein the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; wherein, the positive electrode active material is the high nickel ternary positive electrode material of the embodiment. The negative electrode includes: an anode current collector and an anode material supported on the anode current collector, the anode material comprising: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder. Therefore, the lithium battery has all the characteristics and advantages described above for the high-nickel ternary cathode material, and the description thereof is omitted. In general, the lithium battery has excellent cycle performance and thermal stability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing a high nickel ternary positive electrode material according to one embodiment of the present invention;
FIG. 2 is a graph showing the results of cycle performance tests of batteries fabricated from the positive electrode materials of examples 1-4 and comparative examples.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second", "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," or "third" may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a method of making a high nickel ternary positive electrode material is provided. According to an embodiment of the invention, the method comprises: (1) mixing a high-nickel ternary positive electrode material precursor, a metal oxide and a lithium salt to obtain a mixed material; (2) sequentially carrying out first sintering treatment and second sintering treatment on the mixed material to obtain a first product; (3) mixing the first product with a hydrogen phosphate solution to enable the hydrogen phosphate to wrap the surface of the first product to obtain mixed slurry; (4) adding alkali liquor into the mixed slurry to enable the hydrogen phosphate to have a precipitation reaction and form a coating layer on the surface of the first product, so as to obtain a second product containing the coating layer; (5) and carrying out third sintering treatment on the second product to obtain the high-nickel ternary cathode material.
According to the method for preparing the high-nickel ternary cathode material, firstly, a metal oxide-doped high-nickel ternary cathode material inner core (namely a first product) is prepared by utilizing a high-nickel ternary cathode material precursor, a metal oxide and a lithium salt, then, a hydrogen phosphate is wrapped on the surface of the first product, and then, a hydrogen phosphate substrate on the surface of the first product is wrapped by utilizing an alkali liquor, so that a uniform and continuous phosphorus-containing coating layer is formed, and a second product containing the coating layer is obtained; and sintering to obtain the high-nickel ternary cathode material product with the metal oxide doped core and the phosphorus-containing coating layer. The method can realize that the phosphate layer is uniformly coated on the surface of the high-nickel ternary material, so that the contact between the electrolyte and the anode material is effectively isolated, the generation of NiO cubic phase on the surface layer of the high-nickel ternary anode material and the collapse of the material structure are inhibited, the cycle performance and the thermal stability of the battery are improved, and the method is simple and easy to control in process, strong in operability and easy to industrialize.
A method of preparing a high nickel ternary cathode material according to an embodiment of the present invention is further described in detail below with reference to fig. 1. According to an embodiment of the invention, the method comprises:
s100: obtaining a mixture
In the step, a high-nickel ternary positive electrode material precursor, a metal oxide and a lithium salt are mixed to obtain a mixed material.
The specific kind of the high-nickel ternary positive electrode material precursor is not particularly limitedBy way of limitation, high nickel ternary positive electrode material precursors common in the art may be employed. Therefore, the method provided by the invention is suitable for doping and coating modification of the existing high-nickel ternary cathode material, and better cyclicity and thermal stability are obtained. According to some embodiments of the invention, the high-nickel ternary positive electrode material precursor may be NixCoyMn(1-x-y)(OH)2Or NixCoyAl(1-x-y)(OH)2Wherein, 0.6<x<0.85，0.1≤y<0.2。
According to some embodiments of the present invention, the metal oxide may include one or more selected from MgO and Al2O3And ZrO2At least one of (a). The ternary material core is doped and modified by adopting the metal oxide, so that the cycle performance of the ternary material can be further improved, and the metal oxide and phosphorus in the ternary material surface coating layer generate a synergistic effect, so that the overall electrochemical performance and the thermal stability of the material are further improved.
According to some embodiments of the present invention, the lithium salt may be selected from LiOH, LiNO3And Li2CO3Preferably, at least one of (a) and (b) is LiOH. The lithium salt has wide sources, low cost and easy obtainment, has good compatibility with the precursor of the high-nickel ternary cathode material and the metal oxide, and is suitable for preparing the high-performance metal oxide doped high-nickel ternary cathode material inner core.
According to some embodiments of the present invention, in the step of mixing the high-nickel ternary positive electrode material precursor, the metal oxide and the lithium salt, the molar amount of the metal element and the molar amount of the lithium salt in the high-nickel ternary positive electrode material precursor may be 1 (1.03 to 1.08), such as 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08 and the like, and the molar amount of the metal oxide is 0.001 to 0.1%, such as 0.001%, 0.005%, 0.01%, 0.05%, 0.08%, 0.1% and the like, of the molar amount of the metal element in the high-nickel ternary positive electrode material precursor. The total molar amount of the metal elements in the high-nickel ternary positive electrode material precursor refers to the total molar amount of the various metal elements, that is, the total molar amount of the nickel element, the cobalt element and the manganese element, or the total molar amount of the nickel element, the cobalt element and the aluminum element. The electrochemical performance of the material can be further improved by mixing the high-nickel ternary positive electrode material precursor, the metal oxide and the lithium salt according to the proportion.
According to the embodiment of the invention, the high-nickel ternary positive electrode material precursor, the metal oxide and the lithium salt can be stirred and mixed by a dry method. The mixing conditions include: the temperature can be 20-30 ℃ (such as 20 ℃, 25 ℃, 30 ℃ and the like), the time can be 10-40 min (such as 10min, 20min, 30min, 40min and the like), and the stirring speed can be 800-1200 r/min (such as 800r/min, 900r/min, 1000r/min, 1100r/min, 1200r/min and the like). Under the conditions, the precursor of the high-nickel ternary cathode material, the metal oxide and the lithium salt are stirred and mixed by a dry method, so that the mixing uniformity of all components can be further improved, and the formation of the core of the high-nickel ternary cathode material and the doping of the metal oxide to the core of the high-nickel ternary cathode material are further facilitated.
S200: first and second sintering processes
In this step, the mixed material is subjected to a first sintering treatment and a second sintering treatment in sequence in an oxidizing atmosphere (for example, under pure oxygen conditions) to obtain a first product. Therefore, the doping effect of the metal oxide on the high-nickel ternary cathode material core can be obviously improved by sequentially pre-burning and sintering the mixed materials.
According to some embodiments of the present invention, the first sintering process may be performed at 450-550 ℃ for 4-6 hours, specifically, the temperature of the first sintering process may be 450 ℃, 475 ℃, 500 ℃, 525 ℃, 550 ℃, and the like, and the sintering time may be 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, and the like. The first sintering treatment can be completed at 740-820 ℃ for 13-16 h. Specifically, the temperature of the second sintering treatment can be 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃ and the like, and the sintering time can be 13h, 14h, 15h, 16h and the like. By carrying out the first and second sintering treatments under the above conditions, the formation of the high-nickel ternary cathode material core and the doping of the metal oxide to the core can be further facilitated.
S300: obtaining mixed slurry
In the step, the first product is mixed with a hydrogen phosphate solution, so that the hydrogen phosphate is coated on the surface of the first product, and the mixed slurry is obtained.
The specific kind of the above hydrogen phosphate is not particularly limited, and those skilled in the art can select the hydrogen phosphate according to actual needs. According to some embodiments of the invention, the hydrogen phosphate salt comprises a compound selected from LiH2PO4、Al(H2PO4)3And NaH2PO4At least one of (a). The hydrogen phosphate can be uniformly and continuously coated on the surface of the core of the high-nickel ternary cathode material in the form of solution.
According to some embodiments of the invention, the concentration of the above-mentioned hydrogen phosphate solution may be 15.0 to 20.0 wt%, such as 15.0 wt%, 16.0 wt%, 18.0 wt%, 20.0 wt%. If the concentration of the hydrogen phosphate solution is too low, the concentration of the hydrogen phosphate coated on the surface of the core of the high-nickel ternary cathode material is too low, and the formed coating layer is uneven and discontinuous. If the concentration of the hydrogen phosphate solution is too high, the solution may have too high a viscosity, be difficult to handle, and the phosphorus content of the resulting coating may be difficult to control.
According to some embodiments of the invention, the mass ratio of the hydrogen phosphate solution to the first product (high-nickel ternary positive electrode material core) may be (1-10): 90-100. Specifically, the parts by mass of the hydrogen phosphate solution may be 1, 3, 5, 7, 10, etc., and the parts by mass of the first product may be 90, 92.5, 95, 97.5, 100, etc. Preferably, the mass ratio of the hydrogen phosphate solution to the first product is 5: 95. Therefore, the coating effect of the hydrogen phosphate solution on the high-nickel ternary cathode material inner core can be further improved, and the formation of a uniform and continuous phosphorus-containing coating layer is further facilitated. If the dosage of the phosphate solution is too large, the thickness of a phosphorus-containing coating layer formed subsequently can be too large, and the electrical property of the material is influenced.
According to some embodiments of the invention, the mixing conditions include: the temperature is 30-50 deg.C (such as 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, etc.), the time is 20-30 min (such as 20min, 25min, 30min, etc.), and the stirring speed is 500-700 r/min (such as 500r/min, 600r/min, 700r/min, etc.). Therefore, the coating effect of the hydrogen phosphate solution on the high-nickel ternary cathode material inner core can be further improved, and the formation of a uniform and continuous phosphorus-containing coating layer is further facilitated.
In addition, it should be noted that the specific form of providing the hydrogen phosphate solution is not particularly limited, and for example, the hydrogen phosphate solid may be mixed with water to prepare a solution; alternatively, the metal may be reacted with phosphoric acid to form hydrogen phosphate to obtain a hydrogen phosphate solution.
S400: forming a coating layer
In the step, alkali liquor is added into the mixed slurry, so that the hydrogen phosphate is subjected to precipitation reaction and a coating layer is formed on the surface of the first product, and a second product containing the coating layer is obtained. In some embodiments, the step is performed in a stirring tank, and the alkali liquor is added under the condition of stirring the mixed slurry, so that the nucleation of the core of the high-nickel ternary cathode material and the growth of the surface coating layer of the core are balanced, and a well-combined, uniform and continuous coating layer is formed. Preferably, the alkali liquor is added into the mixed slurry in a slow dropwise manner, and the specific dropwise adding rate can be 10-50 mL/min, for example. If the alkali liquor is directly added, the problems of flocculent precipitate, unstable combination of coating layers, bare ternary material inner cores and the like can be caused in the mixed materials. If the dropping speed of the alkali liquor is too fast, the nucleation of the material can be too fast, the growth of crystal nucleus is not facilitated, and flocculent precipitate is easy to form.
According to some embodiments of the present invention, the alkali solution may include at least one selected from the group consisting of an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution. Preferably, the alkali solution is an aqueous lithium hydroxide solution. By using the lithium hydroxide aqueous solution, the hydrogen phosphate salt can be precipitated to form a coating layer without introducing other impurities into the system.
S500: third sintering treatment
In the step, in an oxidizing atmosphere (for example, under the condition of pure oxygen), the second product is subjected to a third sintering treatment, so that the phosphorus-containing coating layer is stably combined on the surface of the core of the high-nickel ternary cathode material, and the high-nickel ternary cathode material product is obtained.
According to some embodiments of the present invention, the third sintering process is performed at 450-500 ℃ for 4.5-5.5 hours. Specifically, the temperature of the third sintering treatment may be 450 ℃, 475 ℃, 500 ℃ and the like, and the sintering time may be 4.5h, 5h, 5.5h and the like. By performing the third sintering treatment under the above conditions, the stability of the clad layer can be further improved.
According to some embodiments of the present invention, the method for preparing a high-nickel ternary cathode material further comprises, before S500: and washing, filtering and drying the second product in sequence. Therefore, impurities such as residual free alkali on the surface of the second product can be effectively removed, and the quality of the product obtained by subsequent sintering is further improved.
According to some embodiments of the invention, the washing filtration comprises: and washing the second product until the pH value of the filtrate is 6-7. Therefore, the effect of removing impurities such as residual free alkali on the surface of the second product is better.
According to some embodiments of the present invention, the drying may be performed at 80-120 ℃ for 16-20 hours. Specifically, the drying temperature may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ and the like, and the drying time may be 16h, 17h, 18h, 20h and the like. By drying the washed and filtered second product under the above conditions, the water in the second product can be effectively removed, and the second product is not damaged due to overhigh drying temperature or overlong drying time.
In another aspect of the invention, a high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the high-nickel ternary cathode material is prepared by the method for preparing the high-nickel ternary cathode material in the embodiment. Therefore, the high-nickel ternary cathode material is provided with a metal oxide doped and modified high-nickel ternary cathode material core and a phosphorus-containing coating layer, the phosphorus-containing coating layer can effectively isolate the electrolyte from contacting with the cathode material, inhibit the generation of NiO cubic phase on the surface layer of the high-nickel ternary cathode material and the collapse of a material structure, and generate a synergistic effect with the metal oxide doping in the core, so that the cycle performance and the thermal stability of the battery are improved. In addition, it should be noted that all the features and advantages described above for the method for preparing the high-nickel ternary cathode material are also applicable to the high-nickel ternary cathode material, and are not described in detail herein.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes: a positive electrode, a negative electrode, a separator and an electrolyte; wherein the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; wherein, the positive electrode active material is the high nickel ternary positive electrode material of the embodiment. The negative electrode includes: an anode current collector and an anode material supported on the anode current collector, the anode material comprising: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder. Therefore, the lithium battery has all the characteristics and advantages described above for the high-nickel ternary cathode material, and the description thereof is omitted. In general, the lithium battery has excellent cycle performance and thermal stability.
According to some embodiments of the present invention, the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected according to actual needs. The specific types of the positive electrode conductive agent and the positive electrode binder are not particularly limited, and for example, the positive electrode conductive agent may be at least one of common positive electrode binders such as conductive carbon black SP or ECP, carbon nanotubes (CNT or WCNT), graphene, and the like; the positive electrode binder may be at least one of common positive electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. The positive electrode material may further include a common solvent (e.g., NMP) for mixing the positive electrode material, and the ratio of the solvent to the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected by those skilled in the art according to actual needs.
According to some embodiments of the present invention, the mass ratio of the above-described anode active material, anode conductive agent, and anode binder to the thickening stabilizer is not particularly limited and may be selected according to actual needs. The specific types of the negative electrode active material, the negative electrode conductive agent and the negative electrode binder are not particularly limited, and the negative electrode active material can be at least one of common negative electrode active materials selected from natural graphite, artificial graphite, mesophase microspheres, soft carbon, hard carbon and the like; the negative electrode conductive agent can be at least one of conductive carbon black SP or ECP, carbon nano tube (CNT or WCNT), graphene and other common negative electrode conductive agents; the negative electrode binder may be at least one of common negative electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. In addition, the negative electrode material may further include a common solvent (e.g., NMP, deionized water, etc.) for mixing the negative electrode material, and the solvent is not particularly limited and may be selected by those skilled in the art according to actual needs.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) High nickel Ni0.8Co0.1Mn0.1(OH)2Materials with LiOH, ZrO2And carrying out dry mixing to obtain a mixed material. Wherein, the mixing proportion is as follows: high nickel Ni0.8Co0.1Mn0.1(OH)2The ratio of the total mole amount of Ni, Co and Mn to the mole amount of LiOH in the material is 1:1.05, ZrO is added2The molar quantity of the doped metal element is high nickel Ni0.8Co0.1Mn0.1(OH)2The dry mixing of 0.01-0.1% of the total mole amount of Ni, Co and Mn in the material is carried out at 20-30 ℃ and at a stirring speed of 800 r/min.
(2) Presintering the mixed material for 5h at 500 ℃ under the condition of pure oxygen, and then sintering for 16h at 780 ℃ to obtain a doped high-nickel ternary material, namely a first product;
(3) LiH with the concentration of 20 wt%2PO4Mixing the aqueous solution and the first product according to a mass ratio of 5:95, and stirring for 30min in a water bath at 30 ℃ at a rotating speed of 400r/min to obtain mixed slurry;
(4) dissolving LiOH with the concentration of 15 wt% in water according to the molar ratio of LiOH to LiH2PO4Slowly dripping the solution 2:1 into the mixed slurry, stirring for 2.5h at the temperature of 30 ℃ and the rotating speed of 600r/min, carrying out suction filtration and washing until the pH value of the filtrate is 6-7, and then carrying out vacuum drying for 20h at the temperature of 80 ℃ to obtain the coating layer containing Li3PO4The high nickel NCM material of (a), the second product;
(5) and sintering the second product under the pure oxygen condition, wherein the sintering temperature is 480 ℃, and the sintering time is 4.5h, so as to obtain the high-nickel ternary cathode material product.
Example 2
(1) High nickel Ni0.8Co0.1Mn0.1(OH)2Materials with LiOH, ZrO2And carrying out dry mixing to obtain a mixed material. Wherein, the mixing proportion is as follows: high nickel Ni0.8Co0.1Mn0.1(OH)2The ratio of the total mole amount of Ni, Co and Mn to the mole amount of LiOH in the material is 1:1.05, ZrO is added2The molar quantity of the doped metal element is high nickel Ni0.8Co0.1Mn0.1(OH)2The dry mixing of 0.01-0.1% of the total mole amount of Ni, Co and Mn in the material is carried out at 20-30 ℃ and at a stirring speed of 800 r/min.
(2) Presintering the mixed material for 5h at 500 ℃ under the condition of pure oxygen, and then sintering for 16h at 780 ℃ to obtain a doped high-nickel ternary material, namely a first product;
(3) al (H) with a concentration of 20 wt%2PO4)3Mixing the aqueous solution and the first product according to a mass ratio of 5:95, and stirring for 30min in a water bath at 30 ℃ at a rotating speed of 400r/min to obtain mixed slurry;
(4) dissolving LiOH with the concentration of 15 wt% in water according to a molar ratio of LiOH to Al (H)2PO4)3Slowly dripping the solution 2:1 into the mixed slurry, stirring for 2.5h at the temperature of 30 ℃ and the rotating speed of 600r/min, carrying out suction filtration and washing until the pH value of the filtrate is 6-7, and then carrying out vacuum drying for 20h at the temperature of 80 ℃ to obtain the coating layer containing Li3PO4The high nickel NCM material of (a), the second product;
(5) and sintering the second product under the pure oxygen condition, wherein the sintering temperature is 480 ℃, and the sintering time is 4.5h, so as to obtain the high-nickel ternary cathode material product.
Example 3
(1) High nickel Ni0.8Co0.1Mn0.1(OH)2Materials with LiOH, ZrO2And carrying out dry mixing to obtain a mixed material. Wherein, the mixing proportion is as follows: high nickel Ni0.8Co0.1Mn0.1(OH)2The ratio of the total mole amount of Ni, Co and Mn to the mole amount of LiOH in the material is 1:1.05, ZrO is added2The molar quantity of the doped metal element is high nickel Ni0.8Co0.1Mn0.1(OH)2The dry mixing of 0.01-0.1% of the total mole amount of Ni, Co and Mn in the material is carried out at 20-30 ℃ and at a stirring speed of 800 r/min.
(2) Presintering the mixed material for 5h at 500 ℃ under the condition of pure oxygen, and then sintering for 16h at 780 ℃ to obtain a doped high-nickel ternary material, namely a first product;
(3) NaH with the concentration of 20 wt%2PO4Mixing the aqueous solution and the first product according to a mass ratio of 5:95, and stirring for 30min in a water bath at 30 ℃ at a rotating speed of 400r/min to obtain mixed slurry;
(4) dissolving LiOH with the concentration of 15 wt% in water according to the molar ratio of LiOH to NaH2PO4Slowly dripping the solution 2:1 into the mixed slurry, stirring for 2.5h at the temperature of 30 ℃ and the rotating speed of 600r/min, carrying out suction filtration and washing until the pH value of the filtrate is 6-7, and then carrying out vacuum drying for 20h at the temperature of 80 ℃ to obtain the coating layer containing Li3PO4The high nickel NCM material of (a), the second product;
(5) and sintering the second product under the pure oxygen condition, wherein the sintering temperature is 480 ℃, and the sintering time is 4.5h, so as to obtain the high-nickel ternary cathode material product.
Example 4
(1) High nickel Ni0.8Co0.1Mn0.1(OH)2Materials with LiOH, ZrO2And carrying out dry mixing to obtain a mixed material. Wherein, the mixing proportion is as follows: high nickel Ni0.8Co0.1Mn0.1(OH)2Ni, Co in the material,The ratio of the total molar amount of Mn to the molar amount of LiOH is 1:1.05, ZrO2The molar quantity of the doped metal element is high nickel Ni0.8Co0.1Mn0.1(OH)2The dry mixing of 0.01-0.1% of the total mole amount of Ni, Co and Mn in the material is carried out at 20-30 ℃ and at a stirring speed of 800 r/min.
(2) Presintering the mixed material for 5h at 500 ℃ under the condition of pure oxygen, and then sintering for 16h at 780 ℃ to obtain a doped high-nickel ternary material, namely a first product;
(3) LiH with a concentration of 15 wt%2PO4Mixing the aqueous solution and the first product according to a mass ratio of 5:95, and stirring for 30min in a water bath at 30 ℃ at a rotating speed of 400r/min to obtain mixed slurry;
(4) dissolving 20 wt% LiOH in water according to a molar ratio of LiOH to LiH2PO4Slowly dripping the solution 2:1 into the mixed slurry, stirring for 2.5h at the temperature of 30 ℃ and the rotating speed of 600r/min, carrying out suction filtration and washing until the pH value of the filtrate is 6-7, and then carrying out vacuum drying for 20h at the temperature of 80 ℃ to obtain the coating layer containing Li3PO4The high nickel NCM material of (a), the second product;
(5) and sintering the second product under the pure oxygen condition, wherein the sintering temperature is 480 ℃, and the sintering time is 4.5h, so as to obtain the high-nickel ternary cathode material product.
Comparative example
(1) High nickel Ni0.8Co0.1Mn0.1(OH)2Materials with LiOH, ZrO2And carrying out dry mixing to obtain a mixed material. Wherein, the mixing proportion is as follows: high nickel Ni0.8Co0.1Mn0.1(OH)2The ratio of the total mole amount of Ni, Co and Mn to the mole amount of LiOH in the material is 1:1.05, ZrO is added2The molar quantity of the doped metal element is high nickel Ni0.8Co0.1Mn0.1(OH)2The dry mixing of 0.01-0.1% of the total mole amount of Ni, Co and Mn in the material is carried out at 20-30 ℃ and at a stirring speed of 800 r/min.
(2) And pre-burning the mixed material for 5h at 500 ℃ under the pure oxygen condition, and then sintering for 16h at 780 ℃ to obtain a doped high-nickel NCM ternary material product.
Test example
The high-nickel ternary positive electrode material products prepared in examples 1-4 and the comparative example are respectively prepared into button batteries for testing, and cycle performance tests are carried out, wherein the test results are shown in fig. 2. The test result shows that the battery made of the NCM811 material doped and coated by the method of the invention is obviously superior to the battery made of the commercial NCM811 material in cycle performance.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a high-nickel ternary cathode material is characterized by comprising the following steps of:
(1) mixing a high-nickel ternary positive electrode material precursor, a metal oxide and a lithium salt to obtain a mixed material;
(2) sequentially carrying out first sintering treatment and second sintering treatment on the mixed material to obtain a first product;
(3) mixing the first product with a hydrogen phosphate solution to enable the hydrogen phosphate to wrap the surface of the first product to obtain mixed slurry;
(4) adding alkali liquor into the mixed slurry to enable the hydrogen phosphate to have a precipitation reaction and form a coating layer on the surface of the first product, so as to obtain a second product containing the coating layer;
(5) and carrying out third sintering treatment on the second product to obtain the high-nickel ternary cathode material.
2. The method of claim 1, wherein the high-nickel ternary positive electrode material precursor is NixCoyMn(1-x-y)(OH)2Or NixCoyAl(1-x-y)(OH)2Wherein, 0.6<x<0.85，0.1≤y<0.2；
Optionally, the metal oxide comprises a metal selected from MgO, Al2O3And ZrO2At least one of;
optionally, the lithium salt comprises a material selected from LiOH, LiNO3And Li2CO3At least one of (a).
3. The method according to claim 1, wherein the molar ratio of the total amount of the metal elements in the high-nickel ternary positive electrode material precursor to the molar amount of the lithium salt is 1 (1.03-1.08), and the molar amount of the metal oxide is 0.001-0.1% of the total amount of the metal elements in the high-nickel ternary positive electrode material precursor.
4. The method of claim 1, wherein in step (1), the mixing conditions comprise: the temperature is 20-30 ℃, the time is 10-40 min, and the stirring speed is 800-1200 r/min;
optionally, in step (3), the mixing conditions include: the temperature is 30-50 ℃, the time is 20-30 min, and the stirring speed is 500-700 r/min.
5. The method of claim 1, wherein the first sintering treatment is performed at 450-550 ℃ for 4-6 hours, and the second sintering treatment is performed at 740-820 ℃ for 13-16 hours.
6. The method of claim 1, wherein the hydrogen phosphate salt comprises a material selected from the group consisting of LiH2PO4、Al(H2PO4)3And NaH2PO4At least one of;
optionally, the concentration of the hydrogen phosphate solution is 15.0-20.0 wt%;
optionally, the mass ratio of the hydrogen phosphate solution to the first product is (1-10): 90-100);
optionally, the alkali solution includes at least one selected from the group consisting of an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution.
7. The method of claim 1, wherein the third sintering treatment is performed at 450 to 500 ℃ for 4.5 to 5.5 hours.
8. The method of claim 1, further comprising, prior to step (5): washing, filtering and drying the second product in sequence;
optionally, the washing filtration comprises: washing the second product until the pH value of the filtrate is 6-7;
optionally, the drying is carried out for 16-20 h at 80-120 ℃.
9. A high-nickel ternary cathode material, which is prepared by the method of any one of claims 1 to 8.
10. A lithium battery, comprising: a positive electrode, a negative electrode, a separator and an electrolyte; wherein,
the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; wherein the positive electrode active material is the high-nickel ternary positive electrode material according to claim 9.
The negative electrode includes: an anode current collector and an anode material supported on the anode current collector, the anode material comprising: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422925A (en) * | 2020-03-31 | 2020-07-17 | 蜂巢能源科技有限公司 | High-nickel ternary cathode material, preparation method thereof, lithium ion battery and electric automobile |
| CN112382741A (en) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion secondary battery |
| CN113764633A (en) * | 2021-07-21 | 2021-12-07 | 广西师范大学 | Surface modified lithium ion battery positive electrode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104300135A (en) * | 2014-09-18 | 2015-01-21 | 秦皇岛中科远达电池材料有限公司 | Nickel-rich concentration gradient type lithium nickel cobalt aluminum oxide positive pole material, preparation method thereof and lithium ion battery |
| CN105336927A (en) * | 2015-09-28 | 2016-02-17 | 深圳市贝特瑞新能源材料股份有限公司 | Modified super-hydrophobic material-coated lithium ion battery high-nickel cathode material and preparation method thereof |
| US20180183045A1 (en) * | 2016-12-28 | 2018-06-28 | Sichuan FuHua New Energy High-Tech Co., LTD. | High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof |
| CN109950498A (en) * | 2019-03-29 | 2019-06-28 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof with uniform clad |
| CN109994728A (en) * | 2019-03-29 | 2019-07-09 | 宁波容百新能源科技股份有限公司 | The one nickelic positive electrode and preparation method thereof with uniform clad |
| CN110224133A (en) * | 2019-07-12 | 2019-09-10 | 昆山宝创新能源科技有限公司 | Nickelic tertiary cathode material and its preparation method and application |
-
2019
- 2019-11-07 CN CN201911081744.XA patent/CN110844945A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104300135A (en) * | 2014-09-18 | 2015-01-21 | 秦皇岛中科远达电池材料有限公司 | Nickel-rich concentration gradient type lithium nickel cobalt aluminum oxide positive pole material, preparation method thereof and lithium ion battery |
| CN105336927A (en) * | 2015-09-28 | 2016-02-17 | 深圳市贝特瑞新能源材料股份有限公司 | Modified super-hydrophobic material-coated lithium ion battery high-nickel cathode material and preparation method thereof |
| US20180183045A1 (en) * | 2016-12-28 | 2018-06-28 | Sichuan FuHua New Energy High-Tech Co., LTD. | High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof |
| CN109950498A (en) * | 2019-03-29 | 2019-06-28 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof with uniform clad |
| CN109994728A (en) * | 2019-03-29 | 2019-07-09 | 宁波容百新能源科技股份有限公司 | The one nickelic positive electrode and preparation method thereof with uniform clad |
| CN110224133A (en) * | 2019-07-12 | 2019-09-10 | 昆山宝创新能源科技有限公司 | Nickelic tertiary cathode material and its preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422925A (en) * | 2020-03-31 | 2020-07-17 | 蜂巢能源科技有限公司 | High-nickel ternary cathode material, preparation method thereof, lithium ion battery and electric automobile |
| CN111422925B (en) * | 2020-03-31 | 2023-01-20 | 蜂巢能源科技有限公司 | High-nickel ternary cathode material, preparation method thereof, lithium ion battery and electric automobile |
| CN112382741A (en) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion secondary battery |
| WO2022078300A1 (en) * | 2020-10-12 | 2022-04-21 | 深圳市贝特瑞纳米科技有限公司 | Positive electrode material, preparation method therefor, and lithium ion secondary battery |
| CN113764633A (en) * | 2021-07-21 | 2021-12-07 | 广西师范大学 | Surface modified lithium ion battery positive electrode material and preparation method thereof |
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